CN108250674A - A kind of halogen-free epoxy resin composition and use its prepreg and laminate - Google Patents

A kind of halogen-free epoxy resin composition and use its prepreg and laminate Download PDF

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Publication number
CN108250674A
CN108250674A CN201611232856.7A CN201611232856A CN108250674A CN 108250674 A CN108250674 A CN 108250674A CN 201611232856 A CN201611232856 A CN 201611232856A CN 108250674 A CN108250674 A CN 108250674A
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China
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epoxy resin
halogen
weight
parts
active ester
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CN201611232856.7A
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Chinese (zh)
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何烈相
曾宪平
徐浩晟
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201611232856.7A priority Critical patent/CN108250674A/en
Priority to PCT/CN2017/082801 priority patent/WO2018120563A1/en
Publication of CN108250674A publication Critical patent/CN108250674A/en
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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
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    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The present invention provides a kind of halogen-free epoxy resin composition and use its prepreg and laminate.The halogen-free epoxy resin composition includes：(A) halogen-free epoxy resin and (B) phosphorous active ester resin.Using prepreg and laminate made of this halogen-free epoxy resin composition, there is high-fire resistance, low-k, low dielectric loss factor, high humidity resistance and low water absorption, and can realize halogen-free flameproof.

Description

A kind of halogen-free epoxy resin composition and use its prepreg and laminate
Technical field
The invention belongs to copper-clad plate technical fields, and in particular to a kind of halogen-free epoxy resin composition and pre- using it Leaching material, laminate and printed circuit board.
Background technology
All the time, laminate for printed circuits generally use halogen flame reaches fire-retardant purpose, but halogen flame In burning, not only smoke amount is big, and the smell is awful, and can generate the very strong hydrogen halide of corrosivity.It is another it has been reported that The carcinogens such as bioxin, dibenzofurans can be generated when halogen-containing fire retardant is in Pintsch process and burning in recent years, because This, with European Union《It is instructed about electric/electronic device is scrapped》With《Harmful substance is used about being limited in electric/electronic device Instruction》Formally implement on July 1st, 2006, the emphasis for being developed into industry of halogen-free flame-retardant laminate for printed circuits.
On the other hand, with electronic component towards, small-size light-weight slimming, high performance, multifunction direction hair Exhibition, bring therewith be high frequency, high speed signal transmission.In addition to this, humidity resistance and water suction of the high multi-layer PCB board because of CCL Property difference caused by be layered plate bursting problem, cause great concern.
CN105392817A, CN104204031A, CN103965588A etc. have synthesis or even with phosphorous active esters Resin combination, but it cannot keep the flat of high-fire resistance, low-k, low dielectric loss factor and high humidity resistance Weighing apparatus.
For this purpose, how while keeping composition that there is high-fire resistance, the dielectric constant that has had both, dielectric loss factor With high humidity resistance and low water absorption, and it can realize that halogen-free flameproof is the technical issues of this field is urgently to be resolved hurrily.
Invention content
The problem of for prior art, the purpose of the present invention is to provide a kind of halogen-free epoxy resin composition and uses Its prepreg and laminate.It is normal with high-fire resistance, low dielectric using the laminate that the halogen-free epoxy resin composition manufactures The advantages of number, low dielectric loss factor, high humidity resistance and low water absorption, and can realize halogen-free flameproof.
The present inventor has carried out in-depth study repeatedly to achieve the above object, as a result, it has been found that：By by epoxy resin and The phosphorous active ester resin of special construction and other compositions that optionally component is suitably mixed to get, can reach above-mentioned purpose.
For this purpose, present invention employs following technical solutions：
First, the present invention provides a kind of phosphorous active ester resins, have the structure as shown in formula (I)：
Wherein, A and A1It is each independently selected fromIn any one；
P1, q1, m1 and n1 represent repetitive unit, and wherein p1, q1 is each independently the integer more than or equal to 1, such as 1, 2nd, 3,4,5 or 6 and more than；M1, n1 represent average degree of polymerization, 0 ＜ m1≤3, for example, m1 can be 0.25,1,1.2,2,2.5 or 3, m1 can not be with for 0；0≤n1≤3, such as n1 can be 0,0.25,0.5,1,1.2,2,2.6 or 3；
Z is-CH2、In any one；
R is any one in hydrogen, aliphatic functional group or aromatic series functional group；
X is
Y isOr derivatives thereof or formula (In) shown in Structure：
Formula (In) in, YnAnd Yn' be each independently selected from Or derivatives thereof or formula (In+1) shown in structure, n be >=4 positive integer, p2, q2, m2 and n2 represent repetitive unit, wherein P2, q2 are each independently the integer more than or equal to 1, for example, 1,2,3,4,5 or 6 and more than；M2, n2 expression average degree of polymerization, 0 ＜ m2≤3, such as m2 can be that 0.25,1,1.2,2,2.5 or 3, m2 can not be with for 0；0≤n1≤3, for example, n1 can be 0, 0.25th, 0.5,1,1.2,2,2.6 or 3；B is 0~2 integer, such as 1 or 2.
Between the number-average molecular weight of the phosphorous active ester resin with formula (a) structure is 500~5000, such as can be with It is 500,600,700,800,900,1200,1500,2100,2800,3000,3500,4100,4500 or 5000 and above-mentioned Specific point value between numerical value, as space is limited and for it is concise the considerations of, the present invention no longer range described in exclusive list includes Specific point value.
In phosphorous active ester resin of the present invention with formula (a) structure, formula (In) it is not a specific general formula, when n is 4 When, formula (II4) in have branch Y4And Y4', and Y4And Y4' be each independently respectively Or derivatives thereof or formula (I5) shown in structure；Formula (I at this time5) in have branch Y5And Y5', and Y5And Y5' be each independently respectively ForOr derivatives thereof or formula (I6) shown in structure；... (with this several cycle), Formula (In) in have branch YnAnd Yn', and YnAnd Yn' be each independently respectivelyOr Its derivative or formula (In) shown in structure；But for the phosphorous active ester resin formula (I with formula (a) structuren) structure Be unable to Infinite Cyclic, when by cycle reach molecular weight for 500~5000 when, hydrogen atom may be used and blocked.
The present invention uses phosphorous active ester resin, has preferable bridging property compared to common phosphorus containing phenolic resin, can improve Crosslink density, reactivity and glass transition temperature with epoxy resin.Again because having in its structure with not having after epoxy reaction The ester group of secondary hydroxyl makes it with high-fire resistance, low-k, low dielectric loss factor, high humidity resistance and low suction The advantages of water rate and realization halogen-free flameproof.
Preferably, the phosphorous active ester resin has the following structure：
Wherein, A and A1It is each independently selected fromIn any one；
P1, q1, m1 and n1 represent repetitive unit, and wherein p1, q1 is each independently the integer more than or equal to 1, m1, n1 table Show average degree of polymerization, m1, n1 are the arbitrary number between 0.25~3；
Z isR is hydrogen；X is
Y1、Y2And Y3It is each independently selected fromOr formula (In) shown in structure：
Formula (In) in, YnAnd Yn' be each independently selected fromOr formula (In+1) shown in structure, n For >=4 positive integer, p2, q2, m2 and n2 represent repetitive unit, and wherein p2, q2 is each independently the integer more than or equal to 1, M2, n2 represent average degree of polymerization, and m2, n2 are the arbitrary number between 0.25~3；B is 0~2 integer；
Between the number-average molecular weight of the phosphorous active ester resin with formula (a) structure is 500~5000.
The present invention also provides a kind of halogen-free epoxy resin composition, including following component：
(A) halogen-free epoxy resin；
(B) foregoing phosphorous active ester resin.
By using foregoing phosphorous active ester resin in the present invention, do not generated after being reacted with halogen-free epoxy resin Secondary hydroxyl, moreover it is possible to make it have high-fire resistance, low-k, low dielectric loss factor, high humidity resistance, low water absorption and The advantages of realizing halogen-free flameproof.
According to the present invention, the addition of the halogen-free epoxy resin can be obviously improved the heat resistance of solidfied material and curing is crosslinked Density can specifically be selected from biphenyl novolac epoxy resin, DCPD types novolac epoxy resin, alkylidene novolac epoxy resin, double Phenol A types novolac epoxy resin, bisphenol f type epoxy resin, bisphenol Z type epoxy resin, bisphenol-ap type epoxy resin, bis-phenol TMC types Epoxy resin, containing biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresols phenol Novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, Dicyclopentadiene-phenol add Into response type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthols aralkyl type epoxy Resin, naphthols-phenol copolycondensation phenolic resin varnish type epoxy resin, naphthols-cresols copolycondensation phenolic resin varnish type epoxy resin, fragrance Race's hydrocarbon formaldehyde resin phenol-formaldehyde resin modified type epoxy resin, biphenyl modified novolac type epoxy resin or imide-modified epoxy In resin any one or at least two mixture, wherein typical but non-limiting mixture is：Biphenyl phenolic aldehyde ring Oxygen resin and DCPD types novolac epoxy resin, alkylidene novolac epoxy resin and bisphenol A-type novolac epoxy resin, bisphenol-ap type ring Oxygen resin and bis-phenol TMC type epoxy resin.
Preferably, the halogen-free epoxy resin is biphenyl novolac epoxy resin, DCPD types novolac epoxy resin or bisphenol A-type In novolac epoxy resin any one or at least two mixture.
It is highly preferred that the halogen-free epoxy resin is biphenyl novolac epoxy resin or/and DCPD type novolac epoxy resins, The heat resistance and dielectric properties having had both.
In accordance with the present invention it is preferred that the parts by weight of the halogen-free epoxy resin and phosphorous active ester resin, by Halogen epoxy The ester group equivalent proportion of the epoxide equivalent of resin and phosphorous active ester resin is 1:(0.9~1.1) is calculated, preferably the two ratio It is 1:(0.95~1.05), such as 1:0.9、1:0.95、1:1、1:1.05 or 1:1.1, preferably 1:(0.95~1.05), Yi Jishang State the specific point value between numerical value, as space is limited and for it is concise the considerations of, no longer range described in exclusive list of the invention includes Specific point value.
In the present invention, the halogen-free epoxy resin composition can also include crosslinking agent, and crosslinking agent can effectively be promoted and ring The crosslinking curing effect of oxygen resin.
According to the present invention, using the additive amount of halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent as 100 parts by weight Meter, the additive amount of the crosslinking agent are 11~37 parts by weight, for example, 11 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight or 37 weights Measure the specific point value between part and above-mentioned numerical value, as space is limited and for it is concise the considerations of, the present invention no longer exclusive list institute State the specific point value that range includes, preferably 24~37 parts by weight.
According to the present invention, the crosslinking agent is for any one in active ester, anhydride compound or phenolic resin or extremely Mixture two kinds few, wherein typical but non-limiting crosslinking agent is active ester and anhydride compound, anhydride compound or phenol Urea formaldehyde.
Preferably, the active ester is the active ester crosslinking agent with functional group's ester group, and anhydride compound can be benzene second The compounds such as alkene maleic anhydride, phenolic resin can be linear phenolic resin, xenol phenolic resin, alkylphenol phenolic resin, The phenolic resin of the hydroxyls such as DCPD phenolic resin.
It is further preferred that the crosslinking agent is active ester work/and anhydride compound, with respect to phenolic resin, have more Good dielectric properties.
It is highly preferred that the crosslinking agent is the active ester having the following structure, due to the special construction of the active ester, wherein The rigid structures such as phenyl ring, naphthalene nucleus, cyclopentadiene assign the active ester high heat resistance, simultaneously because the regularity of its structure and With being generated in epoxy resin reaction process without secondary hydroxyl, its good electrical property and low water imbibition are assigned.
X is phenyl or naphthalene, j be 0 or 1, k be 0 or 1, n expression repetitive unit be 0.25~1.25, such as 0.25, 0.5th, the specific point value between 0.75,1,1.05 or 1.25 and above-mentioned numerical value, as space is limited and for it is concise the considerations of, this The specific point value that range described in invention no longer exclusive list includes.
In the present invention, the halogen-free epoxy resin composition can also further comprise cyanate or its prepolymer, can carry The glass transition temperature of composition is risen, while N-P cooperative flame retardants are realized with phosphorous active ester resin, improves flame retarding efficiency.
Preferably, the cyanate can be the cyanate containing at least two cyanato- in bisphenol A cyanate ester equimolecular Compound or and its prepolymer, can preferably promote the glass transition temperature of composition.
The sum of additive amount by the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent is institute in terms of 100 parts by weight The additive amount for stating cyanate or its prepolymer is 10~20 parts by weight, such as 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 weights Measure the specific point value between part, 18 parts by weight or 20 parts by weight and above-mentioned numerical value, as space is limited and for it is concise the considerations of, The present invention specific point value that no longer range described in exclusive list includes.
Preferably, the halogen-free epoxy resin composition further includes curing accelerator, makes resin solidification and accelerates resin Curing rate.
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 weight Part meter, the additive amount of the curing agent accelerating agent are 0.05~1 parts by weight, such as 0.05 parts by weight, 0.1 parts by weight, 0.15 weight Measure part, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 weight Part, 0.55 weight, 0.60 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, Specific point value between 0.9 parts by weight or 1 parts by weight and above-mentioned numerical value, as space is limited and for it is concise the considerations of, the present invention The specific point value that no longer range described in exclusive list includes.
Preferably, the curing accelerator is 4-dimethylaminopyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e)s or 2- In phenylimidazole, zinc Isoocatanoate any one or at least two mixture.
To further improve the fire retardant characteristic of halogen-free epoxy resin composition, in preferable situation, the present invention still choosing At least one specific fire-retardant compound of selecting property addition.
Preferably, the halogen-free epoxy resin composition may also include fire-retardant compound, and the fire-retardant compound is Anti-flammability salt, such as phosphate compounds or nitrogenous phosphate compounds, it is not limited to this.
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 weight Part meter, the additive amount of the fire-retardant compound are 0~50 parts by weight, such as 1 parts by weight, 5 parts by weight, 10 parts by weight, 15 weights Measure part, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight and above-mentioned Specific point value between numerical value, as space is limited and for it is concise the considerations of, the present invention no longer range described in exclusive list includes Specific point value.
Preferably, the halogen-free epoxy resin composition can also include filler, and the filler is organic or/and inorganic fill out Material, is mainly used to adjust some physical property effects of composition, such as reduces coefficient of thermal expansion (CTE), reduces water absorption rate and raising Thermal conductivity etc..
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 weight Part meter, the additive amount of the filler are 0~100 parts by weight, such as 0.5 parts by weight, 1 parts by weight, 5 parts by weight, 10 parts by weight, 15 Parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 weight Part, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight or Specific point value between 100 parts by weight and above-mentioned numerical value, as space is limited and for it is concise the considerations of, no longer limit of the invention Enumerate the specific point value that the range includes, preferably 0~50 parts by weight.
Preferably, the inorganic filler is fused silica, powdered quartz, spherical silica, hollow two Silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, carbonic acid In calcium, calcium silicates, mica or glass fiber powder any one or at least two mixture, wherein typical but nonrestrictive Mixture be：Fused silica and powdered quartz, spherical silica and hollow silicon dioxide, aluminium hydroxide and Aluminium oxide, talcum powder and aluminium nitride, boron nitride and silicon carbide, barium sulfate and barium titanate, strontium titanates and calcium carbonate.
Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder Kind or at least two mixture, wherein typical but nonrestrictive mixture is：Polytetrafluorethylepowder powder and polyphenylene sulfide gather Ether sulfone powder and polytetrafluorethylepowder powder, polyphenylene sulfide and polyether sulfone powder, poly- polyphenylene sulfide and polyether sulfone powder.
Preferably, the filler is silica, and angle value is 1~15 μm in the grain size of filler, in the grain size of preferred filler Angle value is 1~10 μm.
" comprising " of the present invention, it is intended that it can also include other components, these other components in addition to the component Assign the halogen-free epoxy resin composition different characteristics.In addition to this, " comprising " of the present invention, may be replaced by Enclosed " for " or " by ... form ".
For example, the halogen-free epoxy resin composition can also contain various additives, as concrete example, can enumerate anti- Oxygen agent, heat stabilizer, antistatic agent, ultra-violet absorber, pigment, colorant or lubricant etc..These various additives can be with It is used alone, two kinds or two or more can also be used in mixed way.
The conventional production method of the halogen-free epoxy resin composition of the present invention：A container is taken, is first put into solid component, so After add in liquid flux, after stirring is until be completely dissolved, adds in liquid resin, filler, fire retardant and curing accelerator, continue to stir It mixes uniformly, glue finally is made with solvent adjustment liquid solid content to 60%~80%.
The present invention also provides a kind of prepreg, including reinforcing material and by adhering to thereon as above after being impregnated with drying The halogen-free epoxy resin composition.
Illustrative reinforcing material such as adhesive-bonded fabric or/and other fabrics, for example, natural fiber, organic synthetic fibers and Inorfil.
Using fabrics or organic fabrics such as glue impregnation reinforcing material such as glass cloth, the reinforcing material being impregnated with is existed Heat drying can obtain prepreg in 5~10 minutes in 155~170 DEG C of baking oven.
The present invention also provides a kind of laminate, including an at least prepreg as described above.
The present invention also provides a kind of printed circuit board, including an at least prepreg as described above.
Compared with prior art, the present invention has the advantages that：
(1) phosphorous active ester resin in the present invention, can be as the curing agent of epoxy resin, and can provide halogen-free flameproof Characteristic, and because having in its structure and not having the ester group of secondary hydroxyl after epoxy reaction, phosphorus containing phenolic resin can be obviously improved Humidity resistance is poor, dielectric constant, the problems such as dielectric loss factor is excessively high, and relative to existing phosphorous active ester resin, with Epoxy resin reaction is easy, and crosslink density is big, and composition is made to have higher glass transition temperature and better humidity resistance, It significantly improves and phosphorus containing phenolic resin and active ester is used to sacrifice the dielectric constant of part as co-curing epoxy resin, be situated between Outside the problems such as electrical loss factor and water absorption rate, it can not still be obviously improved the too low situations of composition Tg；
(2) prepreg, laminate and the metal-clad laminate made using the halogen-free epoxy resin composition has height The advantages of high-fire resistance, low-k, low dielectric loss factor, high humidity resistance and low water absorption, and can realize that Halogen hinders Combustion.
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.
According to above-mentioned made halogen-free epoxy resin composition metal-clad laminate, its glass transition temperature is tested Degree, dielectric constant, dielectric loss factor, PCT and PCT water absorption rates, flammability, such as following embodiments are added on detailed description with retouching It states, wherein the mass parts of organic resin are based on organic solid quality part.
Preparation example 1：It is prepared by phosphorous active ester resin B 1
1mol phosphorus-containing phenolic aldehydes are added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender DHP-60H (Jiangsu Yoke Technology Co., Ltd.'s trade name) and 816g methyl iso-butyl ketone (MIBK)s (MIBK), will depressurize in system Nitrogen is replaced, and makes its dissolving.Then, 0.9mol paraphthaloyl chlorides are put into, react 2h, in system temperature control 60 DEG C with Under；Then, 1.2mol phenol, the reaction was continued 1h are added in into system；Under logical condition of nitrogen gas, 20% hydrogen-oxygen of 189g is slowly added dropwise Change sodium water solution；Continue stirring 1 hour under this condition.After reaction, static liquid separation removes water layer.In reactant dissolving Water is put into MIBK phases, is stirred, static liquid separation removes water layer.Aforesaid operations are repeated until the PH of water layer reaches 7.0 left sides It is right.Then moisture is sloughed by decanter, MIBK is sloughed in then vacuum distillation, obtains active ester resin B 1.
Preparation example 2：It is prepared by phosphorous active ester resin B 2
Throwing 260g phenol, 200g 4,4' dihydroxy diphenyls, 648 grams of formalins in a kettle, (mass concentration is 37%) temperature is heated to 40 DEG C, keeps the temperature 3 hours with 24g sodium hydroxides, unlatching stirring.65 DEG C are then heated to, heat preservation 3 is small Shi Hou adds in 1480g n-butanols, flows back 12 hours.Material temperature is down to 55-60 DEG C, and is evaporated under reduced pressure and is removing 1000g or so just Butanol obtains intermediate.
1080g DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) are added in into intermediate, it is small 2 When interior material temperature liter is gradually warming up to 190 DEG C from 80 DEG C, and apply decompression to system to ensure that n-butanol is arranged in time at 120 DEG C Go out system.1 hour is kept the temperature at 180 DEG C, material temperature is then down to 135 DEG C, the propylene glycol monomethyl ether of 900g or so is added in, continues to stir It mixes 0.5 hour, blowing, obtains phosphorus system curing agent A2.
1mol A2 and 816g are added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender Methyl iso-butyl ketone (MIBK) (MIBK) will depressurize nitrogen displacement, make its dissolving in system.Then, 0.9mol paraphthaloyl chlorides are put into, 2h is reacted, temperature control is below 60 DEG C in system；Then, 1.2mol phenol, the reaction was continued 1h are added in into system；Logical nitrogen Under the conditions of, 20% sodium hydrate aqueous solution of 189g is slowly added dropwise；Continue stirring 1 hour under this condition.After reaction, it is quiet Only liquid separation removes water layer.Water is put into the MIBK phases of reactant dissolving, is stirred, static liquid separation, removes water layer.In repetition Operation is stated until the PH of water layer reaches 7.0 or so.Then moisture is sloughed by decanter, MIBK is sloughed in then vacuum distillation, is obtained To active ester resin B 2.
Embodiment 1
A container is taken, the NC-3000H and 28 parts by weight EF-40 for adding in 100 parts by weight add in suitable MEK, stirring and dissolving Afterwards, the phosphorous active ester resin and the FB-3Y of the 79 parts by weight and BYK- of 0.79 parts by weight in 55 parts by weight preparation examples 1 are added in W903, stirring, adds in suitable curing accelerator DMAP, continues to stir evenly, with solvent adjustment liquid solid content extremely finally 60%~70% and glue is made.Impregnate above-mentioned glue with glass fabric, glue.Above-mentioned glue is impregnated with glass fabric Liquid, and control to suitable thickness, then drying removes solvent and obtains prepreg.It is mutually folded using the prepreg obtained by several It closes, covers a copper foil respectively in its both sides, put curing in hot press into and the epoxy resin copper-clad plate lamination plate is made.Object Property data are as shown in table 1.
Implementation column 2~14：
Manufacture craft and implementation column 1 are identical, and formula composition and its physical index are as shown in table 1~2.
Comparative example 1~6：
Manufacture craft is same as Example 1, and formula composition and its physical index are as shown in table 3.
Table 1
Table 2
Table 3
Note：In table all in terms of solid component parts by weight.
The material enumerated in table 1~3 is specific as follows：
B1：The phosphorous active ester resin of preparation example 1.
B2：The phosphorous active ester resin of preparation example 2.
92741：Phosphorus containing phenolic resin (Dow trade names).
NC-3000H：Biphenyl novolac epoxy resin (the Japanization pharmacist name of an article).
7200-3H：DCPD types novolac epoxy resin (DIC trade names).
627：Bisphenol A-type novolac epoxy resin (U.S.'s Hexion trade names).
HPC-8000-65T：Active ester curing agent (Japanese DIC trade names).
EF-40：Maleic anhydride of styrene (Sartomer trade name).
2812：Linear phenolic resin (South Korea's Momentive trade names).
CE01PS：Bisphenol A cyanate ester (Yangzhou apocalypse commodity chemical name).
525：Silica filler (silicon is than section trade name).
BYK-W903：Filler dispersant (BYK trade names).
DMAP：Curing accelerator, 4-dimethylaminopyridine (wide honor commodity chemical name).
Zinc Isoocatanoate：Curing accelerator (AlfaAesar trade name).
The test method of more than characteristic is as follows：
(1) glass transition temperature (Tg)：According to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institutes Defined DSC method is measured.
(2) dielectric constant and dielectric loss factor：Method according to IPC-TM-650 2.5.5.9 defineds is tested, Test frequency is 10GHz.
(3) PCT and PCT water absorption rates：After the copper foil etching that copper-clad plate is shown, substrate is evaluated：By substrate placement force pot In, under the conditions of 120 DEG C, 105KPa, handle 6 hours：It is impregnated in afterwards in 288 DEG C of tin stove, when base material is layered, records phase Between seasonable：It can terminate to evaluate when substrate does not occur bubble or layering also in tin stove more than 5min.
(4) flammability：According to UL94 law regulations.
Physical Property Analysis：
From the physical data of table 1~3 it is found that in comparative example 1~6, comparative example 3 is existed using existing phosphorus containing phenolic resin PCT is layered plate bursting, and dielectric constant, dielectric loss factor and humidity resistance are poor and glass transition temperature is low；Comparative example 2 is using existing Some active ester resins, although improving dielectric properties and humidity resistance problem, it can not provide halogen-free flameproof, and Tg is very It is low；And comparative example 1, it is combined using the resin combination of comparative example 2 and 3, although providing halogen-free flameproof, it can not be in synthesis Balance is realized in performance, and its Tg, Dk/Df, PCT characteristic and PCT water absorption rates are worse relative to embodiment 11, comparative example 4 and ratio Compared with example 5 compared with embodiment 11~13 it is found that when 4 and 5 halogen-free epoxy resin of comparative example and phosphorous active ester parts by weight not by When being calculated according to epoxy resin equivalent and the ester group equivalent weight range of phosphorous active ester, plank curing can be caused insufficient, Tg, Dk/Df, PCT water absorption rate are poor with respect to embodiment 11~13, and PCT layering plate burstings occur, and comparative example 6 is using the ring without filler Oxygen resin+phosphorus containing phenolic resin+active ester resin, although providing halogen-free flameproof, it can not realize flat in comprehensive performance Weighing apparatus, and its Tg, Dk/Df, PCT characteristic and PCT water absorption rates are worse relative to the similary embodiment 14 without filler.
In addition, embodiment 1~14 using halogen-free epoxy resin and phosphorous active ester resin or its be total to other optional components The composition of mixed composition, has both high-fire resistance, low-k, low dielectric loss factor, high humidity resistance and low water absorption Advantage, and can realize halogen-free flameproof；From embodiment 6 and embodiment 8 it is found that by the B1 compositions formed Tg highers, it is comprehensive It can be more preferable.
As described above, compared with general laminate, Halogen circuit board of the invention is normal with high-fire resistance, low dielectric Number, low dielectric loss factor, high humidity resistance and low water absorption and it can realize halogen-free flameproof.
The above, only presently preferred embodiments of the present invention, for those of ordinary skill in the art, can basis Technical scheme of the present invention and technical concept make other various corresponding changes and deformation, and all these changes and deformation are all The range of the claims in the present invention should be belonged to.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.

Claims (10)

1. a kind of phosphorous active ester resin, which is characterized in that the phosphorous active ester resin has the structure as shown in formula (a)：
Wherein, A and A1It is each independently selected fromIn any one；
P1, q1, m1 and n1 represent repetitive unit, and wherein p1, q1 is each independently the integer more than or equal to 1, and m1, n1 represent flat Homopolymerization is right, 0 ＜ m1≤3,0≤n1≤3；
Z is-CH2-、In any one；
R is any one in hydrogen, aliphatic functional group or aromatic series functional group；
X is
Y1、Y2And Y3It is each independently selected fromOr derivatives thereof, Or formula (In) shown in structure：
Formula (In) in, YnAnd Yn＇ is each independently selected from Or its Derivative or formula (In+1) shown in structure, n is >=4 positive integer, and p2, q2, m2 and n2 represent repetitive unit, wherein p2, q2 The integer more than or equal to 1 is each independently, m2, n2 represent average degree of polymerization, 0 ＜ m2≤3,0≤n2≤3；B be 0~2 it is whole Number；
Between the number-average molecular weight of the phosphorous active ester resin with formula (a) structure is 500~5000.
2. phosphorous active ester resin as described in claim 1, which is characterized in that the phosphorous active ester resin has following knot Structure：
Wherein, A and A1It is each independently selected fromIn any one；
P1, q1, m1 and n1 represent repetitive unit, and wherein p1, q1 is each independently the integer more than or equal to 1, and m1, n1 represent flat Homopolymerization is right, and m1, n1 are the arbitrary number between 0.25~3；
Z isR is hydrogen；X is
Y1、Y2And Y3It is each independently selected fromOr formula (In) shown in structure：
Formula (In) in, YnAnd Yn＇ is each independently selected fromOr formula (In+1) shown in structure, n be >=4 Positive integer, p2, q2, m2 and n2 represent repetitive unit, and wherein p2, q2 be each independently the integer more than or equal to 1, m2, n2 Represent average degree of polymerization, m2, n2 are the arbitrary number between 0.25~3；B is 0~2 integer；
Between the number-average molecular weight of the phosphorous active ester resin with formula (a) structure is 500~5000.
3. a kind of halogen-free epoxy resin composition, which is characterized in that the halogen-free epoxy resin composition includes following component：
(A) halogen-free epoxy resin；
(B) the phosphorous active ester resin described in claims 1 or 2.
4. halogen-free epoxy resin composition as claimed in claim 3, which is characterized in that the halogen-free epoxy resin is xenol Formaldehyde epoxy resin, DCPD types novolac epoxy resin, alkylidene novolac epoxy resin, bisphenol A-type novolac epoxy resin, bisphenol-f type Epoxy resin, bisphenol Z type epoxy resin, bisphenol-ap type epoxy resin, bis-phenol TMC types epoxy resin, containing biphenyl type epoxy resin, Tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenyl methane Type epoxy resin, tetraphenyl ethane type epoxy resin, Dicyclopentadiene-phenol addition reaction-type epoxy resin, phenol aralkyl Type epoxy resin, naphthol novolac type epoxy resin, naphthols aralkyl-type epoxy resin, naphthols-phenol copolycondensation phenolic aldehyde are clear Paint shaped epoxy resin, naphthols-cresols copolycondensation phenolic resin varnish type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin epoxy-type Any one in epoxy resin, biphenyl modified novolac type epoxy resin or imide modified epoxy resin or at least two The mixture of kind；
Preferably, the halogen-free epoxy resin is biphenyl novolac epoxy resin, DCPD types novolac epoxy resin or bisphenol A-type phenolic aldehyde In epoxy resin any one or at least two mixture, preferably biphenyl novolac epoxy resin or/and DCPD type phenolic aldehyde Epoxy resin；
Preferably, the parts by weight of the halogen-free epoxy resin and phosphorous active ester resin, by the epoxide equivalent of halogen-free epoxy resin Ester group equivalent proportion with phosphorous active ester resin is 1:(0.9~1.1) is calculated, and preferably the two ratio is 1:(0.95~ 1.05)。
5. the halogen-free epoxy resin composition as described in claim 3 or 4, which is characterized in that the halogen-free epoxy resin combination Object further includes crosslinking agent；
Preferably, the crosslinking agent is any one in active ester, anhydride compound or phenolic resin or at least two Mixture；
Preferably, the crosslinking agent is the active ester having the following structure：
Wherein, X is phenyl or naphthyl, and j is 0 or 1, k are 0 or 1, n represent repetitive unit, is 0.25~1.25；
Preferably, it is counted using the additive amount of halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent as 100 parts by weight, the friendship Join the additive amount of agent for 11~37 parts by weight, preferably 24~37 parts by weight.
6. the halogen-free epoxy resin composition as described in one of claim 3-5, which is characterized in that the halogen-free epoxy resin group It closes object and further includes cyanate or its prepolymer；
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 parts by weight The additive amount of meter, the cyanate or its prepolymer is 10~20 parts by weight；
Preferably, the halogen-free epoxy resin composition further includes curing accelerator；
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 parts by weight Meter, the additive amount of the curing accelerator is 0.05~1 parts by weight；
Preferably, the curing accelerator is 4-dimethylaminopyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e)s or 2- phenyl In imidazoles or zinc Isoocatanoate any one or at least two mixture.
7. the halogen-free epoxy resin composition as described in one of claim 3-6, which is characterized in that the halogen-free epoxy resin group It closes object and further includes fire-retardant compound；
Preferably, the fire-retardant compound is anti-flammability salt, preferably phosphate compound or nitrogenous phosphate compounds；
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 parts by weight Meter, the additive amount of the fire-retardant compound is 0~50 parts by weight；
Preferably, the halogen-free epoxy resin composition further includes filler；
Preferably, the filler is organic or/and inorganic filler；
Preferably, with the sum of additive amount of the halogen-free epoxy resin, phosphorous active ester resin and crosslinking agent for 100 parts by weight Meter, the additive amount of the filler are 0~100 parts by weight, preferably 0~50 parts by weight；
Preferably, the inorganic filler is fused silica, powdered quartz, spherical silica, hollow titanium dioxide Silicon, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, silicon In sour calcium or mica or glass fiber powder any one or at least two mixture；
Preferably, the organic filler for any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or At least two mixture；
Preferably, the filler is silica, and angle value is 1~15 μm, preferably 1~10 μm in the grain size of filler.
8. a kind of prepreg, including reinforcing material and by be impregnated with it is dry after adhere to thereon such as one of claim 3-7 institutes The halogen-free epoxy resin composition stated.
9. a kind of laminate, including an at least prepreg as claimed in claim 8.
10. a kind of printed circuit board, including an at least prepreg as claimed in claim 8.
CN201611232856.7A 2016-12-28 2016-12-28 A kind of halogen-free epoxy resin composition and use its prepreg and laminate Pending CN108250674A (en)

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